EP0914486B1 - Substrat de revetement - Google Patents

Substrat de revetement Download PDF

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Publication number
EP0914486B1
EP0914486B1 EP19970908102 EP97908102A EP0914486B1 EP 0914486 B1 EP0914486 B1 EP 0914486B1 EP 19970908102 EP19970908102 EP 19970908102 EP 97908102 A EP97908102 A EP 97908102A EP 0914486 B1 EP0914486 B1 EP 0914486B1
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EP
European Patent Office
Prior art keywords
substrate
substrate surface
coating
layer
coating substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19970908102
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German (de)
English (en)
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EP0914486A1 (fr
Inventor
Michael Goetz
Walter Hotz
Herbert Keppner
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3A Composites International AG
Original Assignee
Alusuisse Technology and Management Ltd
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Publication of EP0914486A1 publication Critical patent/EP0914486A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03921—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/12764—Next to Al-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a coating substrate for thin film coatings for Manufacture of electronic components containing a rolled aluminum product or aluminum alloys, the substrate surface to be coated local Bumps in the form of small holes or small-grained or needle-shaped Has substrate surface elements.
  • the present invention further relates to a method for the production of the coating substrate.
  • electronic components means, for example, electronic thin-film components such as diodes or transistors, and in particular includes solar cells.
  • electronic components means, for example, electronic thin-film components such as diodes or transistors, and in particular includes solar cells.
  • the economic use of such electronic components essentially depends on their manufacturing costs.
  • solar cells essentially solar cells made of amorphous silicon, abbreviated a-Si, or microcrystalline Silicon, abbreviated ⁇ c-Si, or multiple cells from both or one of the two aforementioned Materials.
  • solar cells have compared to solar cells made of crystalline silicon, which are produced in a batch process, for example on Si wafers, one lower efficiency, but their manufacture is compared to the manufacture of Solar cells made of crystalline silicon are much cheaper. Because of the compared to Solar cells with crystalline silicon lower efficiency of a-Si solar cells or ⁇ c-Si, are large-scale, inexpensive to manufacture for their economical use Modules required.
  • EP-A-0 155 758 describes substrates with a photosensitive layer composite containing a-Si for digital image acquisition using coherent laser light, whereby for Avoiding interferences due to layer thickness variations of the layer composite in this way is built up that at least one pair of non-parallel interfaces between the layers arises, so that between these interfaces a layer with a continuous changing layer thickness is created.
  • solar cells made of a-Si or ⁇ c-Si are used for integrated photovoltaic systems which already have a load-bearing structure for the solar cells, a great potential for use on.
  • solar cell modules made of a-Si or ⁇ c-Si by plasma deposition, CVD (chemical vapor deposition), and PVD (physical vapor deposition) processes directly over a large area the facade elements are applied. This means that you need a direct connection to a facade element applied photovoltaic module made of a-Si or ⁇ c-Si only about a quarter of that for production a corresponding module of crystalline silicon necessary primary energy.
  • Such Solar cells can be used in building construction, for example as facade elements, or in vehicle construction, for example as a chassis cladding, and make a significant contribution contribute to the generation of electrical energy.
  • a significant additional advantage of using aluminum coating substrates also results from the ductility of aluminum and its alloys.
  • the ductility on the one hand allows easier rolling and thus the cost-effective production of flat sheets Substrates and on the other hand the embossing, especially the roll embossing Substrate surfaces.
  • the embossing thus allows the production of for certain uses optimized surface structures, such as inverted pyramids or Sawtooth structures in the submicron to millimeter range, for example for photovoltaic applications.
  • the use of aluminum as substrate material for thin film solar cells made of a-Si or ⁇ c-Si is described in DE 35 28 087, the substrate surface being anodized oxide layer produced in oxalic acid is provided as a barrier and insulation layer.
  • the anodic oxide layer is produced using high-purity aluminum substrates needed.
  • CIS copper indium diselenide
  • CIGS copper indium Gallium diselenide
  • these processes are rather unsuitable for Al substrates because they are temperatures near the melting point of aluminum.
  • plasma deposition at low substrate temperatures it can be in excellent places (grain or acicular Surface structures that are in poorer thermal contact with the substrate) too local heating of the substrate surface and thus to a plasma-induced Interdiffusion of, for example, aluminum and silicon.
  • the substrate surface temperature is not or not by the plasma deposition process is only increased insignificantly, because an increased kinetic energy of some surface atoms due to ion bombardment, in the classic sense, cannot be considered increased Temperature.
  • the object of the present invention is to provide an inexpensive coating substrate for thin film coatings for the production of electronic components which Avoids disadvantages of the substrates known from the prior art described above.
  • bumps usually have little thermal contact have with the substrate body, so that during, for example, a plasma deposition can be poorly delivered to the substrate body by energy supplied by ions and consequently leads to a strong, very local overheating of the substrate surface. The local Overheating then leads to accelerated interdiffusion of substrate material elements and coating elements.
  • all local unevenness of the coating substrate according to the invention have a maximum, measured vertically to the substrate surface, which is smaller than 10 ⁇ m and greater than 0.1 ⁇ m.
  • the maximum parallel to the substrate surface The measured extent of each local unevenness is preferably greater than or equal to that corresponding vertical extent.
  • the angle between any surface normal is Flank of each unevenness and the surface normal of the surrounding unevenness Substrate surface from 0 to 88 °, based on a full circle of 360 °.
  • the lacy ones Parts of the local unevenness of the coating substrate according to the invention also show preferably has a radius of curvature of greater than 0.2 ⁇ m.
  • the coating substrate according to the invention enables the complete overgrowth of the existing local unevenness by the deposited Thin film layers, causing the occurrence of short circuits in the on the coating substrate applied thin film components is prevented.
  • the coating substrate according to the invention is, for example, a flat, rolled one Substrate made of aluminum or its alloys. Sheets, strips or are preferred Foils made of aluminum or aluminum alloys.
  • the substrates can also be bodies any shape with an aluminum surface or an aluminum-containing surface his.
  • the coating substrate can also be a composite material, at least has a cover layer made of aluminum or aluminum alloys. As a coating substrate can thus contain a substrate with a surface layer made of pure aluminum essentially aluminum and the commercial impurities, or from Aluminum alloys can be applied.
  • Coating substrates made of pure aluminum can, for example, be an aluminum of a purity of 98.3% by weight and higher, preferably 99.0% by weight and higher and in particular of 99.5 to 99.98 wt .-%, and the rest contain commercial impurities.
  • Wrought aluminum alloys are used for coating substrates made of aluminum alloys prefers. These alloys include, for example, alloys of the AlMg type, AlMn, AlMgSi, AlCuMg and AlZnMg.
  • wrought aluminum alloys can contain: Up to 1.5% by weight of silicon, up to up to 1.0% by weight of iron, up to 4.0% by weight of copper, up to 1.5% by weight of manganese, up to 6.0 % By weight magnesium, up to 7.0% by weight zinc, up to 0.2% by weight titanium, and up to 1.6 % By weight of other elements, balance aluminum.
  • aluminum substrate alloys are AlMg3, AlMg3Si, AlMg5, AlMg5Si, AlMg10 and AlMgSi1.
  • films with a thickness of 5 ⁇ m to 1.5 are expediently used mm, in particular foils with a thickness of 5 ⁇ m to 20 ⁇ m, or strips or sheets Thickness from 0.5 to 50 mm used.
  • Aluminum sheets, strips or foils are preferred a thickness of 0.01 mm to 5 mm and in particular a thickness of 0.05 mm to 3 mm.
  • the substrates according to the invention allow the direct deposition of thin film systems, such as for solar modules, on aluminum surfaces.
  • This enables, for example the direct installation of photovoltaic modules on facade elements made of commercially available Aluminum or from commercially available composite panels with aluminum cover layers (e.g. Plastic core and honeycomb templates).
  • Such photovoltaic facade elements fulfill that high fire protection requirements usual in building construction Silicon solar cells in particular do not release any toxins.
  • the manufacture is the Operation and disposal of photovoltaic modules on aluminum substrates ecologically no problem.
  • Facade elements with directly deposited thin-film solar cells allow on the one hand Use of facades for economical energy generation and enable on the other hand a reduction in the assembly and sealing costs of solar modules.
  • Such facade elements can also be used hybrid, i.e. they can be used as solar panels, Sun protection and can be used as solar cells.
  • the coating substrate according to the invention has an embossed structure at least partially on or in the substrate surface to be coated on.
  • the embossed structure can have a decorative shape or can be designed in this way be that this is the reflection of incident electromagnetic radiation, in particular Light, allows in a predetermined direction of reflection.
  • the stamping structure is preferably produced by roll stamping, for example in the production of the rolled coating substrates in the last rolling pass Roll used with a roll surface having the desired embossed structure becomes; or by structuring the coating.
  • Decorative embossed structures can include logos, advertising texts, trademarks, company names or contain patterns, with embossed patterns, for example, to increase the security against forgery can be used.
  • embossed structures expediently have Structure depths of 1 nm to 1 ⁇ m, preferably between 10 nm and 0.5 ⁇ m. With The term structure depth becomes the largest height difference achieved in an embossing process between structure valley and structure height.
  • Embossed structures for the targeted deflection or scattering of electromagnetic radiation in A predetermined solid angle range can be used, for example, to increase the efficiency used by solar cells.
  • Such embossed structures expediently have Structure depths from 0.5 ⁇ m to 2 mm, preferably from 10 ⁇ m to 1 mm.
  • the embossing pattern can have any shape in itself.
  • the largest, parallel to The extent of the individual elements of the embossed structure measured on the substrate surface expediently from 1 nm to 5 mm, and preferably between 10 nm and 2 mm.
  • the embossed structure preferably has a saw tooth pattern V-shaped trenches.
  • the flanks of the V-trenches are preferably such that both sides are illuminated at all times of the day during the day. For not close to the equator Areas of application, these V-trenches therefore preferably have an asymmetrical shape on.
  • the V-trenches are formed, for example, in such a way that, relative to the surface normal of the Facade element one flank an angle of about 5 to 10 ° and the other flank one Angle from 50 to 60 ° (angle specification always with respect to a full circle of 360 °).
  • the V-trench structure expediently have a structure size in millimeter or in the submillimeter range.
  • Embossed surface structures such as structures in the form of inverted pyramids or surface structures with a sawtooth pattern, for example in the case of photovoltaic modules the effective thickness of the solar cells, so that the absorbency of the Cells increases.
  • the thickness of the thin film solar cell can thus be higher than that of solar cells
  • Substrates without an embossed structure can be reduced, so that firstly expensive semiconductor material saved, secondly the manufacturing process of the solar cells is accelerated and thirdly - im If amorphous silicon modules are used - a reduction in light-induced aging the cell and thus an increased stabilized efficiency can be achieved.
  • the rolled coating substrate can have a barrier layer on the substrate surface to be coated, the barrier layer being a galvanic metal or metal oxide layer, or a layer of Si x Ny , SiC or ZnO, and the layer thickness of the barrier layer being from 100 nm to Is 5 ⁇ m.
  • An aluminum oxide layer for example anodically produced, is preferably suitable as the metal oxide layer.
  • the barrier layer can consist of a conductive material (eg ZnO); in the case of a conventional series connection of the individual cells, an insulating layer must be applied between the actual module and the substrate (eg sol-gel or enamel layer).
  • sol-gel layers we consider sol-gel layers to be layers that are produced using a sol-gel process.
  • the rolled coating substrate on the substrate surface to be coated, a sol-gel or enamel layer as a barrier layer exhibit.
  • the layer thickness of such a barrier layer is, for example, 0.5 up to 250 ⁇ m, expediently 1 to 200 ⁇ m and preferably 1 to 150 ⁇ m.
  • the sol-gel layers have a glass-like character and can be used in addition to the substrate Barrier layer between the substrate and the actual cells also as the front (Isolating) sealing of the cell against weather influences, liquids favoring corrosion (acid rain, bird droppings, etc.).
  • the hail resistance is ensured due to the compact composite of sol-gel layer and cell-substrate.
  • sol-gel layers produced with a sol-gel process can on the one hand be used as Barrier layer between substrate and cell act, on the other hand, they can be introduced infrared reflecting substances in combination with the conductive ZnO back contact can be used as infrared reflecting mirroring. This allows the otherwise used Silver layer can be saved.
  • Enamel layers colored white can serve as a barrier layer act between substrate and cell, on the other hand they can be infrared reflective Substances in combination with the conductive ZnO back contact as infrared reflecting Mirroring can be used. This can remove the otherwise used silver layer be saved.
  • oxide layers are formed which are an isotropic barrier layer with a thickness from 0.01 to 0.5 ⁇ m with a dielectric constant between 5 and 10.
  • the isotropic barrier layer represents a pore-free oxide layer and has a high temperature resistance, as well as increased compared to aluminum or aluminum alloys chemical resistance.
  • Such an isotropic barrier layer prevents or reduces For example, any diffusion of adhesion inhibitors to the aluminum substrate / sol-gel interface. or enamel layer.
  • An additional porous oxide layer with a thickness of 0.1 to 10 ⁇ m can be applied to the outer surface of the isotropic barrier layer.
  • pores that are open towards the surface are provided.
  • a layer thickness of 0.1 to 2 ⁇ m is preferred for the porous oxide layer.
  • the pores preferably have a diameter between 0.03 to 0.15 ⁇ m and a ratio of pore depth to pore diameter between 2 and 60.
  • the porosity is expediently 10 8 to 10 12 pores / cm 2 and preferably between 10 9 to 10 11 pores / cm 2 .
  • Sol-gel layers contain, for example, polymerization products from organically substituted alkoxysiloxanes of the general formula R'Si (OR) 3 or R ' 2 Si (OR) 2 , where R and R 'have the meaning of a nyamic radical.
  • the sol-gel layer can be a polymerization product of organically substituted alkoxy compounds of the general formula X n AR 4-n where A has the meaning of Si, Ti, Zr or Al, X has the meaning of HO-, alkyl-O- or Cl-, R has the meaning of phenyl, alkyl, vinyl, vinyl ester or epoxy ether and n is a number of 1, 2 or 3 means.
  • the sol-gel layers are advantageous directly or indirectly through a sol-gel process applied to the aluminum substrate.
  • a sol-gel process applied to the aluminum substrate.
  • alkoxides and halosilanes mixed and in the presence of water and suitable catalysts hydrolyzed and condensed. After removal of water and solvent, it forms a sol that is applied to the substrate by dipping, spinning, spraying, etc. the sol converting into a gel film, for example under the influence of temperature and / or radiation.
  • silanes are used to form the sol, it is it is also possible to partially replace the silanes with compounds which replace the silicon Contain titanium, zircon or aluminum. This allows the hardness, density and refractive index the sol-gel layer can be varied.
  • the hardness of the sol-gel layer can also be can be controlled by using different silanes, for example by training an inorganic network to control hardness and thermal stability or by using an organic network to control elasticity.
  • a Sol-gel layer, which is classified between the inorganic and organic polymers can be, via the sol-gel process through targeted hydrolysis and condensation of alkoxides, mainly of silicon, aluminum, titanium and zircon on the aluminum substrates be applied. The process creates an inorganic network and additionally, via derivatized silicic acid esters, organic ones Groups are built in, on the one hand for functionalization and on the other hand for training defined organic polymer systems can be used.
  • the sol-gel film also by electro-dip painting based on the principle of cataphoretic deposition an amine and organically modified ceramic.
  • the enamel layers have a melting point in the range from 480 ° C to the melting point or near the melting point of the aluminum substrate. With close to the melting point temperatures between 20 or 10 ° C below the melting point of the aluminum substrate Roger that.
  • Suitable enamel layers are those based on alkali-silico-titanates, optionally with baking temperature-reducing additives, e.g. links such as oxides of lithium, barium, antimony, cadmium, bismuth or vanadium.
  • Enamel layers which are applied to the substrate as frit with additives are preferred by heat treatment or baking in an enamel layer with a thickness of 50 to 200 microns, preferably from 50 to 120 microns and in particular 70 to 100 microns, are transferred.
  • the enamel layer in turn can, for example, consist of a mixture of oxides in the specified Ratios are generated.
  • the oxides are usually fritted, i.e. as a mixture that was ground.
  • This frit can in turn be processed with processing aids, such as boric acid, sodium metasilicate, potassium hydroxide, titanium dioxide and Pigments are added.
  • Typical example of a frit composition contains: 100 Parts frit, about 4 parts boric acid, one part with sodium metasilicate, one part potassium hydroxide, five to fifteen parts of titanium dioxide and one to seven parts of pigment.
  • the enamel may include, for example, a layer, a layer of a frit composition is applied to the substrate surface and baked in one firing process will, i.e. is transferred into the enamel layer.
  • two layers can be used in two Burning processes, three layers in three burning processes, respectively. multiple layers in multiple Burning processes are applied.
  • Other methods of applying layers of enamel consist of the application of two or more frit layers or frit compositions with just one burn.
  • the frit can be, for example, a medium one Grain size of less than 74 microns and conveniently less than 44 microns.
  • the frit can be applied by sprinkling, spraying, dipping, or slurrying become. Other options are electrostatic spraying or electrophoresis. If necessary, the frit, if applied with a suspension aid, must be dried become. After drying, the coated substrate can be placed in an oven the combustion process can be carried out continuously or in stages. Typical Burning times range between 3 and 10 minutes, with burning times between 3 and 6 minutes are preferred. Typical firing temperatures are between 480 and 560 ° C. The burning process can be carried out step by step or continuously.
  • Substrates according to the invention with a barrier layer made of gel or enamel have an extreme smooth surface.
  • Such barrier layers protect the substrate against mechanical, physical, chemical and actinic influences and, for example, against environmental influences largely protected.
  • the surface is smooth, shiny and extremely hard.
  • the barrier layer serves as a diffusion barrier and / or as an electrical insulation layer.
  • the barrier layer faces the free one Surface at least partially an embossed structure.
  • the embossed structure can be a decorative one Have shape or can be designed such that they reflect the incident electromagnetic radiation, in particular light, in a predetermined direction of reflection enables.
  • the configuration of these embossed structures preferably corresponds that of the previously described embossed structures on aluminum substrate surfaces.
  • the stamping structure is produced, for example, by roll stamping, one Roll used with a roll surface having the desired embossed structure becomes.
  • the surface is preferably embossed in a partially solid state of the barrier layer, i.e. the embossing process takes place at Enamel layers as an intermediate process during the baking process and in the case of sol-gel layers in a partially hardened state.
  • the coating substrate according to the invention is preferred for the production of thin-film solar cells made of amorphous, or poly- or micro-crystalline silicon. All such thin-film solar cells are preferably deposited on facade elements. Solar cells usually show when exposed to high temperatures, for example at full Sun exposure, a loss of efficiency. However, this is with the semiconductor materials a-Si and ⁇ c-Si (poly- or micro-crystalline) compared to monocrystalline silicon solar cells much lower and is typically 0.1% / ° K for a-Si: H, for example. This means that when such solar cells are used on facade panels, ventilation is possible the facade to maintain cell efficiency. This loss of efficiency must not, however, limit the lifespan of a solar cell or connected by photovoltaic modules. Life-limiting The effects of such solar cells are only corrosion due to poor encapsulation of photovoltaic modules and interdiffusion of contact materials into the solar cell.
  • the deposition of the semiconductor film from amorphous, hydrogenated silicon and / or from a Alloy of amorphous, hydrogenated silicon on the coating substrate according to the invention is preferably done in a plasma room that contains at least one pair of electrodes and is coupled to a high frequency electrical generator, the coating substrate is connected to a first electrode and is at a distance from the another, second electrode, and one containing at least one silicon compound Gas is introduced into the plasma space, and a plasma between the two electrodes is generated in that an electrical radio frequency energy with a frequency between 10 and 150 MHz is applied.
  • the distance between the substrate according to the invention and the second electrode is preferably between 1 and 3 cm.
  • the ratio between frequency and the distance between substrate and second electrode is more preferably between 30 and 80 MHz / cm.
  • the frequency is very preferably between 30 and 100 MHz and the distance of the substrate according to the invention from the second electrode is between 1 and 2.5 cm.
  • the ratio between the electrical energy radiated into the plasma, which is measured at the terminals of the two electrodes, and the plasma volume present between the electrodes is preferably between 0.02 and 0.2 W / cm 3 .
  • the plasma deposition of the semiconductor film preferably takes place at a pressure between 10 and 50 Pa, the substrate temperature expediently being kept between 150 and 350 ° C.
  • the gas introduced into the plasma space preferably contains silanes, or disilanes and / or higher-order silanes, or silicon tetrafluoride, or hydrogen, or mixtures of these substances.
  • the silane gas is introduced with a flow rate between 0.3 and 2.0 sccm (cm 3 NTP / min) per liter of the internal useful content of the plasma space and preferably approximately 1.2 sccm / liter.
  • the gas introduced into the plasma space can contain other substances such as germanium, hydrogen, argon, germanium tetrafluoride, methane, carbon tetrafluoride, nitrogen, ammonia, phosphines or diboranes.
  • the deposition of a semiconductor film from a silicon is very particularly preferred. Nitrogen alloy.
  • the gas introduced into the plasma space consists of a mixture of silanes and ammonia in a volume ratio between 0.03 and 0.3, and the distance of the substrate according to the invention from the second electrode is between 1 and 3 cm.
  • the object directed to the method is achieved in that the coating substrate surface a chemical gloss process, or a plasma etching process is exposed.
  • Plasma etching involves plasma etching with radicals that are surface-related react and form gaseous components, or physical plasma etching (sputtering), the surface due to e.g. Ar ion bombardment is removed.
  • nucleating agents such as titanium boride.
  • Such nucleating agents usually cause grain-like structures on the surface, which are mostly sharp-edged and after an alkaline or acid surface cleaning lead to trench-like depressions around the com.
  • Such recesses can mostly not be overgrown satisfactorily by plasma-deposited layers that local short circuits in the thin-film elements built onto the substrate surface can arise between the back and front contact.
  • the sharp-edged grains are therefore before the thin film coating rounded off by, for example, ion bombardment in an Ar plasma.
  • this causes Method of better thermal contact of such grain structures with the substrate body, wherein the interdiffusion of coating material and substrate material during the coating process is reduced.
  • Metals generally have a polycrystalline character.
  • Ar ion bombardment of the substrate surface the metal surfaces acquire an essentially amorphous structure.
  • substrate surfaces cause low interdiffusion properties.
  • Another preferred method for preventing sharp-edged depressions according to the invention consists in cleaning the substrate surface by means of a chemical plasma etching process in an atmosphere which does not chemically attack the substrate surface to be coated.
  • An O 2 , SF 6 , O 2 / SF 6 , CF 4 , O 2 / CF 4 or BCl 3 atmosphere is particularly preferred for this purpose.
  • a method in which the coating substrate has a barrier layer is further preferred has, the layer thickness is selected such that the existing local unevenness are completely covered by this barrier layer in such a way that none there are more sharp-edged bumps.
  • the method according to the invention thus brings about a reduction in the interdiffusion of Substrate elements and thin film coating elements and enables the complete Overgrowth of bumps due to the thin film coatings. This will apply allows inexpensive diffusion barriers and insulation layers, such barrier layers a further rounding effect of the substrate surface unevenness cause.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Computer Hardware Design (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Photovoltaic Devices (AREA)
  • Physical Vapour Deposition (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
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Claims (16)

  1. Substrat de revêtement pour revêtements en film mince, pour la préparation de composants électroniques, contenant un produit laminé en aluminium ou alliage d'aluminium, où les irrégularités locales de la surface du substrat à revêtir se présentent sous la forme de petits trous ou d'éléments de type grain fin ou aiguille, de la surface du substrat, caractérisé en ce que pour éviter les sites défectueux dans les composants électroniques, toutes les irrégularités locales présentes à la surface du substrat à revêtir, qui ont une dimension maximale, mesurée verticalement par rapport à la surface du substrat, inférieure à 10 µm et supérieure à 0,1 µm, sont de sorte que :
    a) les flancs des irrégularités locales peuvent être complètement soumis à un dépôt de matériau se produisant perpendiculairement à la surface du substrat, et
    b) la dimension maximale, mesurée parallèlement à la surface du substrat de chaque irrégularité locale est supérieure ou égale à la dimension verticale correspondante.
  2. Substrat de revêtement suivant la revendication 1, caractérisé en ce que les parties pointues des irrégularités locales présentent un rayon de courbure qui est supérieur à 0,2 µm.
  3. Substrat de revêtement suivant la revendication 1 ou 2, caractérisé en ce que le substrat de revêtement consiste en de l'aluminium pur, avec une pureté allant de 98,3 à 99,98% en poids d'Al, ou en des alliages à base d'Al, ou représente un composite avec au moins une couche de couverture en aluminium pur ou en un alliage d'aluminium, où la surface de la couche de couverture forme la surface du substrat à revêtir.
  4. Substrat de revêtement suivant l'une quelconque des revendications 1 à 3, caractérisé en ce que la surface du substrat à revêtir présente une structure estampée, où les éléments individuels de la structure estampée présentent une profondeur d'estampage allant de 1 nm à 1 mm et où la dimension la plus grande, mesurée parallèlement à la surface du substrat des éléments individuels de la structure estampée se situe dans l'intervalle allant de 1 nm à 5 mm.
  5. Substrat de revêtement suivant la revendication 4, caractérisé en ce que la structure estampée présente un schéma en dents de scie non symétrique, avec creux en V, où chaque creux en V présente un flanc raide et un flanc plat et où le flanc raide vis-à-vis de la normale au flanc sur la surface du substrat dans son ensemble, a un angle allant de 2 à 20° et le flanc plat vis-à-vis de cette normale au flanc, un angle allant de 20 à 70°.
  6. Substrat de revêtement suivant l'une quelconque des revendications 1 à 5, caractérisé en ce que la surface du substrat à revêtir présente une couche barrière, où la couche barrière est de préférence une couche galvanique métallique ou d'oxyde métallique, ou une couche en SixNy, SiC ou ZnO et l'épaisseur de couche de la couche barrière se situe dans l'intervalle allant de 100 nm à 5 µm.
  7. Substrat de revêtement suivant l'une quelconque des revendications 1 à 5, caractérisé en ce que la surface du substrat à revêtir présente une couche sol-gel ou en émail comme couche barrière, et l'épaisseur de couche de la couche barrière se situe dans l'intervalle allant de 0,5 à 250 µm.
  8. Substrat de revêtement suivant la revendication 6 ou 7, caractérisé en ce que la couche barrière présente une structure estampée, où les éléments individuels de la structure estampée présentent une profondeur d'estampage allant de 1 nm à 0,8 mm et où la dimension la plus grande, mesurée parallèlement à la surface du substrat des éléments individuels de la structure estampée se situe dans l'intervalle allant de 1 nm à 1 mm.
  9. Substrat de revêtement suivant l'une quelconque des revendications 1 à 8, caractérisé en ce que la surface du substrat présente une cellule solaire à film mince unique ou multiple, en silicium amorphe ou microcristallin, où les cellules solaires à film mince présentent une construction n-i-p, dont la construction présente sur le côté tourné vers la lumière, une couche protectrice supplémentaire en oxyde conducteur, en particulier en ZnO.
  10. Substrat de revêtement suivant la revendication 9, caractérisé en ce que le substrat de revêtement présente une couche miroir réfléchissant les infrarouges, située entre la surface du substrat et les cellules solaires à film mince, en argent/oxyde de zinc.
  11. Substrat de revêtement suivant la revendication 9, caractérisé en ce que le substrat de revêtement présente une couche miroir située entre la surface du substrat et les cellules solaires à film mince, en émail réfléchissant les infrarouges et une couche TCO (Transparent Contactive Oxide), de préférence en ZnO, ITO (oxyde d'indium-étain) ou SnO2.
  12. Substrat de revêtement suivant la revendication 9, caractérisé en ce que le substrat de revêtement présente une couche sol-gel située entre la surface du substrat et les cellules solaires à film mince, avec des propriétés de réflexion des infrarouges, où les propriétés de réflexion des infrarouges sont obtenues par des particules ou substances réfléchissant les infrarouges, piégées dans la couche sol-gel.
  13. Substrat de revêtement suivant la revendication 9, caractérisé en ce que la couche protectrice située sur les cellules solaires à film mince, en un oxyde conducteur, présente sur le côté tourné vers la lumière, une couche protectrice sol-gel supplémentaire.
  14. Procédé de préparation d'un substrat de revêtement suivant l'une quelconque des revendications 1 à 8, caractérisé en ce que la surface d'aluminium à revêtir est soumise à un processus de gravure chimique par plasma dans une atmosphère n'attaquant chimiquement pas la surface du substrat à revêtir, de préférence une atmosphère de O2, SF6, O2/SF6, CF4, O2/CF4 ou BCl3, ou un processus de gravure physique par plasma dans une atmosphère de gaz inerte, de préférence dans une atmosphère de Ar, N2 ou H2.
  15. Procédé de préparation d'un substrat de revêtement suivant la revendication 13, caractérisé en ce que la couche protectrice sol-gel est structurée.
  16. Utilisation du substrat de revêtement suivant la revendication 1, pour la préparation d'éléments photovoltaïques de façade.
EP19970908102 1996-04-03 1997-03-27 Substrat de revetement Expired - Lifetime EP0914486B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH86596 1996-04-03
CH865/96 1996-04-03
CH86596 1996-04-03
PCT/CH1997/000130 WO1997038145A1 (fr) 1996-04-03 1997-03-27 Substrat de revetement

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AT (1) ATE203781T1 (fr)
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CA (1) CA2250535C (fr)
DE (1) DE59704202D1 (fr)
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AU2020597A (en) 1997-10-29
TW589387B (en) 2004-06-01
PT914486E (pt) 2001-11-30
WO1997038145A1 (fr) 1997-10-16
ATE203781T1 (de) 2001-08-15
CA2250535C (fr) 2004-05-18
ES2159391T3 (es) 2001-10-01
EP0914486A1 (fr) 1999-05-12
CA2250535A1 (fr) 1997-10-16
DE59704202D1 (de) 2001-09-06
US6124039A (en) 2000-09-26

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